CN108368258A

CN108368258A - Barrier structure body based on the MPMDT/XT copolyamides with high Tg

Info

Publication number: CN108368258A
Application number: CN201680072747.5A
Authority: CN
Inventors: T.布里福德; M.卡佩洛特; N.杜福勒
Original assignee: Arkema France SA
Current assignee: Arkema France SA
Priority date: 2015-12-18
Filing date: 2016-12-15
Publication date: 2018-08-03
Anticipated expiration: 2036-12-15
Also published as: US11345131B2; KR20180096673A; FR3045640A1; EP3390493A1; CN108368258B; FR3045640B1; WO2017103502A1; EP3390493B1; US20180370208A1; JP2019502000A; JP7393865B2

Abstract

The present invention relates to the barrier structure bodies of storage and/or transport for fluid comprising at least one barrier layer (1) comprising MPMDT/XT copolyamides, wherein：MPMDT is the unit with amide moieties that molar ratio is 5 to 50%, particularly 5 to 45%, preferably 15 to 45%, more preferable 20 to 45%, wherein MPMD is 2 methyl pentamethylene diamines (MPMD) and T represents terephthalic acid (TPA), XT is the unit with main amide moieties that molar ratio is 50 to 95%, particularly 55 to 95%, preferably 55 to 85%, more preferable 55 to 80%, wherein X be C9 to C18, preferably C9, C10, C11 and C12, linear aliphatic diamines, and wherein T is terephthalic acid (TPA), the fusing point of the copolyamide：250℃<T_fIt≤300 DEG C, is measured according to standard ISO 1 1,357 3 (2013).

Description

Barrier structure body based on the MPMDT/XT copolyamides with high Tg

Technical field

The present invention relates to the barrier structure body (barrier based on the MPMDT/XT copolyamides with high Tg Structure), the structure is free of reinforcing fiber.The structure can be made of the polyphthalamide of single layer, or Person includes the layer of the layer and at least one other material of MPMDT/XT polyphthalamides.

The barrier structure body is suitable for the article for fluid storage and/or transport, such as any kind of bottle, tank, appearance Device (container), pipe and storage tank (receptacle).The structure can also be the form of film, and being for example made with the film needs There is the packaging of barrier property to the fluid of such as gas.All these articles show good barrier property, that is to say, that To fluid, particularly automotive fluids, especially very low to the permeability of fuel.

The invention further relates to the MPMDT/XT copolyamides with high Tg to be used to prepare including at least one comprising described The structure of the barrier layer of MPMDT/XT copolyamides, particularly the purposes of multilayer structure making.

The invention further relates to the purposes of these structures and these articles.

Background technology

Regardless of the fluid for transporting or storing in article such as any kind of bottle, tank, container, pipe and storage tank, with stream The all impermeable fluid of the material that body is in direct contact, no matter fluid is liquid or gas.

Therefore, in automotive field and entire field of traffic, the composition of fuel is constantly changing, especially for ecological former Cause, this makes bio-fuel progress into market.These fuel have more advantage.Therefore, it was demonstrated that improve and connect with these fresh fuels The quality of tactile thermoplastic component is most important, such as the pipe for transporting gasoline.

For the reason of the safety and environmental protection, vehicle manufacturers are applied with mechanical property such as antiknock to these pipes and split Property and the flexible and good impact strength under cool condition (- 40 DEG C) and high temperature (125 DEG C), and to hydrocarbon and its addition The low-down permeability of agent, particularly alcohol such as methanol and ethyl alcohol.These pipes must also have to fuel and engine lubricating oil Good resistance.

Application WO 2014/064375 is related to the composition of thermoplastic composite or the group for thermoplastic composite Object is closed, it is at least 90 DEG C and semicrystalline polyamides of the fusing point Tm less than or equal to 280 DEG C to have by glass transition temperature Tg (PA) matrix made of, and the machinery based on the material or structural body parts and the composition of the invention are used for by multiple Component made of condensation material is used for motor vehicle, railway, ocean, road transport, wind-power electricity generation, movement, aviation and aerospace, builds It builds, the purposes of tablet and leisure area.

The composition can be used for manufacturing the mechanical part involved in the application of automotive field, but in this application not Refer to the structure for including the layer to fluid (especially fuel) barrier.In addition, the composition includes always reinforcing fiber.

EP 1 988 113 describes the moulding compound based on 10T/6T copolyamides, has：

- 40 to 95mol% 10T

- 5 to 40% 6T.

EP 1 988 113 does not refer to the barrier property for the structure being made of the layer of these compositions.

EP 1 741 553 describes the multilayer structure making including two or more layers, the two or more layers of packet Include at least one layer (a) comprising (A) aliphatic polyamide and comprising containing at least 60mol% have 9 to 13 carbon atoms Aliphatic diamine and at least 50mol% terephthalic acid (TPA) partially aromatic polyamide layer (b), middle level (b) be internal layer.

EP 1 741 553 does not refer to the barrier property of this kind of structure completely.

EP 1 860 133 describes a kind of resin of partially aromatic polyamide, which includes dicarboxylic acid units (wherein 50 to 100mol% dicarboxylic acid units are aromatic dicarboxylic acid units) and diamine unit (wherein 60 to 100% diamines Unit is the aliphatic diamine unit with 9 to 13 carbon atoms), amine chain end/acid chain end ratio of the partially aromatic polyamide Example is greater than or equal to 6.

9T/9'T (or 8MT/9T) compound especially has been illustrated in EP 1 860 134, and shows when the ratio is small When 6 and especially 4 or smaller, alcohol resistance reduces.

International application WO 10/015786 is related to the copolyamide of formula A/10.T, wherein：

A is selected from the part obtained by amino carboxylic acid, the part obtained by lactams and corresponds to formula (Ca diamines) (Cb (ring) aliphatic diacid) part, wherein a represents the carbon atom number in diamines and b represents the carbon atom number in diacid, and a and b are respectively Between 4 to 36；

It is characterized in that it is less than or equal to 3.5 by the polydispersity index (being denoted as PDI) that gel permeation chromatography measures.

WO 10/015786 does not refer to the barrier property of this kind of structure completely.

WO 2015/159014 describes a kind of method preparing thermoplastic material, and this method includes at least one injection molding Step or the step of be processed by polyamide extruded composition.It is required that larger numbers of polyamide, and although polyamide Composition can be used for preparing single or multi-layer structure body, but does not refer to the structure and be especially copolymerized comprising MXDT/XT The barrier property of the structure of amide.

In addition, in order to improve the temperature tolerance of copolyamide, machinability or improve its impact strength property and its barrier Property, these polyamide still have much room for improvement, especially in terms of crystallinity, crystallization kinetics.

Therefore, it needs to find the polyphthalamide with improved property really, especially in terms of barrier property.

Invention content

Unexpectedly, it has been found that these need the structure by including at least one layer comprising MPMDT/XT polyamide Met, wherein：

" MPMDT " is indicated comprising the amide portion corresponding to 2- methyl pentamethylene diamines and the condensation product of terephthalic acid (TPA) The unit divided,

XT indicates that (it is indicated comprising X (it indicates aliphatic series, araliphatic, alicyclic or aramid residue) and T is corresponded to Terephthalic acid (TPA)) condensation product amide moieties unit.

MPMDT exists with 5 to 50%, preferably 5 to 45%, more preferable 15 to 45% molar content, and wherein MPMD is represented 2- methyl pentamethylene diamines (MPMD) and T represents terephthalic acid (TPA),

XT be with constituted existing for 50 to 95%, preferably 55 to 95%, more preferable 55 to 85% molar content (include, Comprising) the unit of main amide moieties, wherein X is C₉To C₁₈, preferably C₉、C₁₀、C₁₁And C₁₂, linear aliphatic two Amine, and wherein T is terephthalic acid (TPA),

The fusing point of the copolyamide：250℃<T_mIt≤300 DEG C, is measured according to standard ISO 11357-3 (2013),

The structure is free of reinforcing fiber.

Therefore it has been found that initially for these products of composite material application and development, due to its high rigidity (high Tg)/good Machinability (opposite glue low Tm) compromise, also there is better crystalline texture than expected and may be used as barrier layer, That is, in the structure for fluid transport, particularly in multilayer structure making, to fluid, particularly to Vehicle flow Body, particularly to the low-down layer of the permeability of fuel, although amine chain end/acid chain end ratio is particularly less than 5.

In other words, the structure is barrier structure body, in particular selected from bottle, tank, container, pipe, storage tank and film comprising At least one barrier layer (1) for including MPMDT/XT copolyamides as defined above.

The structure of the present invention can be made of the single layer of the polyamide, in this case, not include reinforcing fiber； Or include the layer of layer and at least one other material comprising MPMDT/XT polyamide (therefore be free of reinforcing fiber), it is described extremely Few other layers can include reinforcing fiber.

In the structure of the present invention, including the layer of MPMDT/XT polyamide can also include other polymers.As this The example of a little other polymers, it can be mentioned that polyamide, EVOH, PPS, PPO, makrolon and ABS.

The invention further relates to any kind of bottle, tank, container, pipe and the storage tanks that are manufactured with the above structure.The structure The form that can also be film is for example made with the film and is packed.All these articles all have good barrier property.

The invention further relates to the purposes of these articles and these structures and these articles.

Specific implementation mode

When reading is described below with embodiment, other features, aspect, theme and advantage of the invention will be even more bright It is aobvious.

According to the first aspect of the invention, the present invention relates to including at least one layer for including MPMDT/XT copolyamides (1) structure, wherein：

MPMDT is with 5 to 50%, particularly 5 to 45%, preferably 15 to 45%, more preferable 20 to 45% molar content The existing unit for constituting amide moieties, wherein MPMD represents 2- methyl pentamethylene diamines (MPMD) and T is represented to benzene two Formic acid,

XT is deposited with 50 to 95%, particularly 55 to 95%, preferably 55 to 85%, more preferable 55 to 80% molar content The main amide moieties of composition unit, wherein X is C₉To C₁₈, preferably C₉、C₁₀、C₁₁And C₁₂, linear aliphatic diamines, and Wherein T is terephthalic acid (TPA),

The fusing point of the copolyamide：250℃<T_mIt≤300 DEG C, is measured according to standard ISO 11357-3 (2013), and

In MPMDT and/or XT units, independently of each other, based on the total amount of dicarboxylic acids, up to 30mol%'s Terephthalic acid (TPA) can use other aromatics comprising 6 to 36 carbon atoms, particularly 6 to 14 carbon atoms, aliphatic series or alicyclic Dicarboxylic acids substitutes, and

In MPMDT and/or XT units, independently of each other, based on the total amount of diamines, up to 30mol%'s MPMD and/or X in appropriate circumstances can with comprising 4 to 36 carbon atoms, particularly 6 to 12 carbon atoms other two Amine substitutes, and

It, can be by lactams or amino carboxylic acid no more than 30mol% based on the total amount of monomer in copolyamide It is formed, and

Condition is, based on the total amount of the monomer used in copolyamide, substitutes the list of terephthalic acid (TPA), MPMD and X The summation of body is no more than the concentration of 30mol%, and

Condition is that MPMD is not substituted completely,

The composition is free of reinforcing fiber.

Therefore, the present invention describes at least single layer and its single layer is the structure based on MPMDT/XT.

It is readily apparent that regardless of the replacement currently carried out to diacid and/or diamines, the ratio of MPMDT and XT are equal It is maintained in the range of institute's indicating value.For example, even if when MPMDT diacid and/or diamines substitute, under any circumstance, MPMDT Exist at least 5% or at least 15% or at least 20% molar content, this depends on claimed numberical range.

In the same way, the upper limit of the range of these values is to retain.

Advantageously, the ratio of the amount of the amount of the amine chain end group of the copolyamide/acid chain end group<5, the amine chain end group Amount and the amount of the sour chain group are measured by NMR.

Advantageously, MPMDT exists with 5 to 50% molar content, and XT exists with 50 to 95% molar content.

Advantageously, MPMDT exists with 15 to 45% molar content, and XT exists with 50 to 85% molar content.

Advantageously, MPMDT exists with 20 to 45% molar content, and XT exists with 50 to 80% molar content.

Advantageously, MPMDT exists with 5 to 45% molar content, and XT exists with 55 to 95% molar content.

Advantageously, MPMDT exists with 15 to 45% molar content, and XT exists with 55 to 85% molar content.

Advantageously, MPMDT exists with 20 to 45% molar content, and XT exists with 55 to 80% molar content.

MPMD and/or X can be independently of each other by other diamines defined above, particularly by linear chain or branched chain aliphatic series two Amine, alicyclic diamine or aryl aromatic diamine, which substitute, is up to 30mol%.

For example, linear chain or branched chain aliphatic diamine is selected from Putriscine, 1,5- pentanediamines, 1,6- hexamethylene diamines, 1,8- Octamethylenediamine (OMDA), 1,9-nonamethylene diamine (NMDA), 2- methyl-1s, 8- octamethylenediamines (MODA), 2,2,4- tri-methyl hexamethylenes two Amine (TMHMD), 2,4,4- trimethylhexamethylenediamines (TMHMD), 5- methyl-1s, 9- nonamethylene diamines, 1,11- hendecanes diamines, 2- butyl -2- ethyl -1,5- pentanediamines, 1,12- dodecamethylene diamines, 1,13- tridecane diamines, 1,14- tetradecanes diamines, 1, 16- hexadecanes diamines and 1,18- octadecamethylene diamines.

Alicyclic diamine can be selected from bis- (amino methyl) hexamethylenes (BAC) of cyclohexane diamine, 1,3-, bis- (the amino first of 1,4- Base) hexamethylene (BAC), isophorone diamine, norbornane dimethylamine, 4,4'- diamino-dicyclohexyl methanes (PACM), 2,2- (4,4'- diaminocyclohexyls) propane (PACP) and 3,3'- dimethyl -4,4'- diamino-dicyclohexyl methanes (MACM).

Aryl diamine can be m-xylene diamine.

T can be substituted most by other dicarboxylic acids defined above, particularly by other aromatics, aliphatic series or alicyclic dicarboxylic acid Up to 30mol%.

Aromatic dicarboxylic acid can be selected from naphthalenedicarboxylic acid (NDA) and M-phthalic acid (IPS).

Aliphatic dicarboxylic acid can be selected from adipic acid, suberic acid, azelaic acid, decanedioic acid, heneicosanedioic acid, dodecanedioic acid, Tridecandioic acid, tetracosandioic acid, pentacosandioic acid, hexadecandioic acid (hexadecane diacid), octadecane diacid and dimer (fatty acid) yl.

Alicyclic dicarboxylic acid can be selected from cis- and/or trans-1,4-cyclohexane-dicarboxylic acids and/or cis--and/or anti- - 1,3 hexamethylenes of formula-dicarboxylic acids (CHDA).

MPMD and/or X and/or T can be substituted independently of each other by lactams or amino carboxylic acid and is up to 30mol%.

Lactams and amino carboxylic acid can be selected from caprolactam (CL), α, omega-amino caproic acid, α, omega-amino n-nonanoic acid, α, Omega-amino hendecanoic acid (AUA), lauryl lactam (LL) and α, omega-amino dodecanoic acid (ADA).

Relative to the summation meter of MPMD, X and T monomer, the replacement of most 30mol% be it is possible, either with other two Amine, other diacid, lactams or amino carboxylic acid or its any mixture replacing.

Advantageously, the replacement of the summation meter relative to MPMD, X and T monomer, maximum 20mol% is possible, is either used Other diamines, other diacid, lactams or amino carboxylic acid or its any mixture replacing.

Advantageously, the replacement of the summation meter relative to MPMD, X and T monomer, maximum 10mol% is possible, is either used Other diamines, other diacid, lactams or amino carboxylic acid or its any mixture replacing.

Advantageously, X is C₉To C₁₈Diamines.

Advantageously, X is C₉To C₁₈Diamines, and MPMDT with 5 to 50% molar content exist and XT with 50 to 95% Mole exists.

Advantageously, X is C₉To C₁₈Diamines, and MPMDT with 5 to 45% molar content exist and XT with 55 to 95% Mole exists.

Advantageously, X is C₉To C₁₈Diamines, and MPMDT with 15 to 45% molar content exist and XT with 55 to 85% Mole exist.

Advantageously, X is C₉To C₁₈Diamines, and MPMDT with 20 to 45% molar content exist and XT with 55 to 80% Mole exist.

Advantageously, X is C₉、C₁₀、C₁₁、C₁₂Diamines.

Advantageously, X is C₉、C₁₀、C₁₁、C₁₂Diamines, and MPMDT with 5 to 50% molar content exist and XT with 50 to 95% mole exists.

Advantageously, X is C₉、C₁₀、C₁₁、C₁₂Diamines, and MPMDT with 5 to 45% molar content exist and XT with 55 to 95% mole exists.

Advantageously, X is C₉、C₁₀、C₁₁、C₁₂Diamines, and MPMDT with 15 to 45% molar content exist and XT with 55 Mole to 85% exists.

Advantageously, X is C₉、C₁₀、C₁₁、C₁₂Diamines, and MPMDT with 20 to 45% molar content exist and XT with 55 Mole to 80% exists.

Advantageously, X is C₉Diamines, and MPMDT with 5 to 50% molar content exist and XT with 50 to 95% mole Amount exists.

Advantageously, X is C₉Diamines, and MPMDT with 5 to 45% molar content exist and XT with 55 to 95% mole Amount exists.

Advantageously, X is C₉Diamines, and MPMDT with 15 to 45% molar content exists and XT rubs with 55 to 85% You exist amount.

Advantageously, X is C₉Diamines, and MPMDT with 20 to 45% molar content exists and XT rubs with 55 to 80% You exist amount.

Advantageously, X is C₁₀Diamines, and MPMDT with 5 to 50% molar content exist and XT with 50 to 95% mole Amount exists.

Advantageously, X is C₁₀Diamines, and MPMDT with 5 to 45% molar content exist and XT with 55 to 95% mole Amount exists.

Advantageously, X is C₁₀Diamines, and MPMDT with 15 to 45% molar content exists and XT rubs with 55 to 85% You exist amount.

Advantageously, X is C₁₀Diamines, and MPMDT with 20 to 45% molar content exists and XT rubs with 55 to 80% You exist amount.

Advantageously, X is C₁₁Diamines, and MPMDT with 5 to 50% molar content exist and XT with 50 to 95% mole Amount exists.

Advantageously, X is C₁₁Diamines, and MPMDT with 5 to 45% molar content exist and XT with 55 to 95% mole Amount exists.

Advantageously, X is C₁₁Diamines, and MPMDT with 15 to 45% molar content exists and XT rubs with 55 to 85% You exist amount.

Advantageously, X is C₁₁Diamines, and MPMDT with 20 to 45% molar content exists and XT rubs with 55 to 80% You exist amount.

Advantageously, X is C₁₂Diamines, and MPMDT with 5 to 50% molar content exist and XT with 50 to 95% mole Amount exists.

Advantageously, X is C₁₂Diamines, and MPMDT with 5 to 45% molar content exist and XT with 55 to 95% mole Amount exists.

Advantageously, X is C₁₂Diamines, and MPMDT with 15 to 45% molar content exists and XT rubs with 55 to 85% You exist amount.

Advantageously, X is C₁₂Diamines, and MPMDT with 20 to 45% molar content exists and XT rubs with 55 to 80% You exist amount.

It states " reinforcing fiber " or " fabric reinforcement " and indicates short or long stapled component.Fiber can be continuous, or In the form of unidirectional (UD) or multidirectional (2D, 3D) reinforcer, in the form of fabric, sheet material, web or braided fabric, and can be with Such as it is cut in the form of non-woven fabric (pad) or in the form of felt.

Statement " reinforcing fiber " particularly indicates：

Mineral fibres, especially carbon fiber comprising nanotube or the fiber of carbon nanotube (CNT), carbon nano-fiber or Graphene；Silicon dioxide fibre such as glass fibre, especially E, R or S2 type；Boron fibre；Ceramic fibre, especially silicon carbide are fine Dimension, boron carbide fibre, boron carbonitrides fiber, silicon nitride fiber, boron nitride fiber, basalt fibre；Based on metal and/or its conjunction The fiber or silk of gold；The fiber of metal oxide, especially aluminium oxide (Al₂O₃) fiber；Metalized fibers such as metallized glass The mixture of fiber and metallized carbon fiber or above-mentioned fiber；

Polymerize or polymer fiber, especially：

The fiber of thermosetting polymer, and be more specifically selected from：Unsaturated polyester (UP), epoxy resin, vinyl esters, phenolic aldehyde Resin, polyurethane, cyanoacrylate and polyimides such as bimaleimide resin, or by amine such as melamine and aldehyde such as second The aminoplast that the reaction of dialdehyde or formaldehyde obtains,

The fiber of thermoplastic polymer, and be more specifically selected from：Polyethylene terephthalate (PET) gathers to benzene Dioctyl phthalate butanediol ester (PBT), high density polyolefins such as polyethylene (PE), polypropylene (PP) and PET/PP copolymers or PVOH (polyvinyl alcohol),

Corresponding to the fiber of the polyamide of one of following formula：6,11,12,610,612,66,4.6,

Aramid fiber is (such as) and fiber for example corresponding to the aromatic polyamides of one of following formula：PPDT, MPDI, PAA and PPA, wherein PPD and MPD are p-phenylenediamine and m-phenylene diamine (MPD) respectively, and PAA is Nomex and PPA is poly- O-phthalic Amide,

The fiber of polyamide block copolymer such as polyamide/polyethers, poly(aryl ether ketone) (PARK) such as polyether-ether-ketone (PEEK), The fiber of polyether ketone ketone (PEKK) or polyetherketoneetherketoneketone (PEKEKK),

Or the mixture of above-mentioned fiber.

Therefore, all reinforcing fibers defined above all exclude except the scope of the present invention.

Advantageously, the amount of amine chain end be 5mmol/kg to 100mmol/kg, preferably 20mmol/kg to 80mmol/kg, and Even more preferably 30mmol/kg to 60mmol/kg.

Advantageously, the amount of sour chain end be 5mmol/kg to 100mmol/kg, preferably 20mmol/kg to 80mmol/kg, and Even more preferably 30mmol/kg to 60mmol/kg.

In an advantageous embodiment, the present invention relates to structures as defined above, wherein defined above described Copolyamide according to standard ISO 11357-2:2013 glass transition temperature Tg >=125 DEG C measured, advantageously Tg>125 ℃。

In an advantageous embodiment, the present invention relates to structure as defined above, wherein X is 1,10- decamethylene diamines.

Advantageously, X is 1,10- decamethylene diamines, and MPMDT with 5 to 50% molar content exists and XT is with 50 to 95% Mole exist.

Advantageously, X is 1,10- decamethylene diamines, and MPMDT with 5 to 45% molar content exists and XT is with 55 to 95% Mole exist.

Advantageously, X is 1,10- decamethylene diamines, and MPMDT with 15 to 45% molar content exists and XT is with 55 to 85% Mole exist.

Advantageously, X is 1,10- decamethylene diamines, and MPMDT with 20 to 45% molar content exists and XT is with 55 to 80% Mole exist.

In an advantageous embodiment, the present invention relates to structure as defined above, wherein the copolyamide Other unused diamines of monomer, other dicarboxylic acids or lactams substitute.

Therefore structure that wherein monomer is not substituted has formula MPMDT/XT, without any other diamines, other The presence of dicarboxylic acids, lactams or amino carboxylic acid.

In an advantageous embodiment, the present invention relates to structures as defined above, wherein the layer (1) includes punching Hit modifying agent and/or core-shell type modifying agent.

Term " impact modifying agent " is understood to mean that according to standard ISO-178:2010 flexural modulus measured are less than 100MPa and Tg are less than 0 DEG C (according to standard 11357-2:2013 at the inflection point of DSC thermograms measure) based on polyene The polymer of hydrocarbon, especially polyolefin, optionally with flexural modulus<The PEBA (polyether block amide) of 200MPa is combined.

In the advantageous embodiment, it is somebody's turn to do the polymer based on polyolefin and is therefore present in the copolymerization acyl for constituting layer (1) In amine.

The polyolefin of impact modifying agent can be functionalized or nonfunctionalized, or at least one functionalized poly- The mixture of alkene and/or the polyolefin of at least one nonfunctionalized.

Particularly, part or all of polyolefin carries the functional group selected from carboxylic acid, carboxylic acid anhydrides and epoxide functional group, and And in particular selected from the copolymer (EPR) of ethylene and propylene with rubber elastomer characteristics, the ethylene-the third with rubber elastomer characteristics Alkene-diene copolymers (EPDM) and ethylene/(methyl) alkyl acrylate copolymer, ethylene-higher olefin copolymer, especially Ethylene-octene copolymer or ethylene/alkyl acrylate-maleic anhydride terpolymer.

Advantageously, impact modifying agent is selected from Fusabond F493,Especially Lotader 5500 or Lotader 7500, Escor VA1801 or VA1803, Excelsior E1040, Amplify GR216, Tafmer MH5020 Or or mixtures thereof Orevac IM800；In this case, when it is two kinds of mixture, proportional region 0.1/ 99.9 to 99.9/0.1, preferably 1/2 to 2/1.

For example, impact modifying agent mixture selected from the following：F493/Especially F493/5500 or F493/7500。

Term " core-shell type modifying agent " is also known as " core-shell type copolymer ".

" core-shell type modifying agent " is the fine grain form with elastomer core and at least one thermoplastic shell；Particle Size is usually less than 1 micron, and is advantageously 150 to 500nm.

Different from the impact modifying agent with polyolefin substrate, " core-shell type modifying agent " has acrylic compounds or butadiene Matrix.

It can be mentioned that the example of core include isoprene or dienite, isoprene be no more than 30mol% Vinyl monomer copolymer and butadiene with no more than 30mol% vinyl monomer copolymer.Vinyl monomer Can be styrene, ring-alkylated styrenes, acrylonitrile or (methyl) alkyl acrylate.Another seed nucleus type is by (methyl) acrylic acid The homopolymer of Arrcostab and (methyl) alkyl acrylate and the copolymer of the vinyl monomer no more than 30mol% form.(first Base) alkyl acrylate is advantageously butyl acrylate.Vinyl monomer can be styrene, ring-alkylated styrenes, acrylonitrile, fourth Diene or isoprene.The core of copolymer (A) can be crosslinked completely or partially.It is added in the preparation process of core at least bifunctional Monomer is sufficient；These monomers can be selected from poly- (methyl) acrylate of polyalcohol, such as two (methyl) acrylic acid fourths two Alcohol ester and trimethylol-propane trimethacrylate.Other bifunctional monomers are such as divinylbenzene, trivinylbenzene, third Olefin(e) acid vinyl acetate and vinyl methacrylate.Core can also by introducing wherein, by be grafted or make in the course of the polymerization process Unsaturated functional monomer's (such as unsaturated carboxylic acid anhydrides, unsaturated carboxylic acid and unsaturated epoxide) is introduced for comonomer to hand over Connection.It can be mentioned that example include maleic anhydride, (methyl) acrylic acid and glycidyl methacrylate.

The shell be styrene, ring-alkylated styrenes or methyl methacrylate homopolymer or include at least 70mol%'s The copolymerization of one of these aforementioned monomers and at least one comonomer selected from other aforementioned monomers, vinyl acetate and acrylonitrile Object.Shell can also introduce unsaturated function list by introducing wherein, by being grafted or being used as in the course of the polymerization process comonomer Body (such as unsaturated carboxylic acid anhydrides, unsaturated carboxylic acid and unsaturated epoxide) is functionalized.It can be mentioned that example include Maleic anhydride, (methyl) acrylic acid and glycidyl methacrylate.For example, it is mentioned that having polystyrene The nuclear-shell copolymer (A) of shell and the nuclear-shell copolymer (A) with PMMA shells.There is also tool, there are two the nuclear-shell copolymers of shell (A), a shell is made of polystyrene and shell is made of PMMA.The example of copolymer (A) and the method record for preparing it In following patent：US 4 180 494, US 3 808 180, US 4 096 202, US 4 260 693, US 3 287 443, US 3 657 391, US 4 299 928, US 3 985 704.

Therefore, " core-shell type modifying agent " is different from the polyolefin of impact modifying agent, in particular, in that impact modifying agent can with it is poly- Amide substrate reaction, and core-shell structure copolymer does not react with it then, is only reacted with its shell because the nuclear energy of the latter is enough.

Advantageously, the weight meter relative to all the components of the copolyamide of layer (1), impact modifying agent and/or core-shell type The amount of modifying agent is 5 to 35 weight %, especially 5 to 25 weight %, and more particularly 5 to 15 weight %.

Advantageously, present invention is accordingly directed to structures as defined above comprising at least one layer (1), layer (1) packet Containing MPMDT/XT copolyamides as defined above and include the ratios of weight meter of all the components relative to copolyamide it is 5 To the impact modifying agent and/or core-shell type modifying agent of 35 weight %, especially 5 to 25 weight %, and more particularly 5 to 15 weights Measure %.

Advantageously, in the structure comprising impact modifying agent and/or core-shell type modifying agent, X is 1,10- decamethylene diamines.

In an advantageous embodiment, the present invention relates to structures as defined above, wherein the structure is by list Layer (1) composition.

Therefore, the present invention is related to mono-layer tube in this case, and other layers are not present in this embodiment.

In an advantageous embodiment, the present invention relates to structures as defined above, wherein the layer (1) includes choosing From stabilizer below：Organic stabilizer, inorganic stabilizers, particularly the stabilizer based on copper and its mixture.

" organic stabilizer " or the more generally main anti-oxidant of " combination of organic stabilizer " expression phenols type are stated, it is sub- The secondary antioxidant of phosphate type or even optionally other stabilizers, such as HALS, mean hindered amine light stabilizer (example Tinuvin 770 such as from Ciba companies), UV stabilizer (such as Tinuvin 312 from Ciba companies), phenols stablize Agent or stabilizer based on phosphorus.The antioxidant of amine type, such as the Naugard from Crompton companies can also be used 445 or multifunctional stabilizers, such as the Nylostab S-EED from Clariant companies.

The organic stabilizer being present in layer (1) can be selected from the case where not limited by the list：

Phenol antioxidant, such as the Irganox 245 from Ciba companies, Irganox 1010, Irganox 1098, the Irganox MD1024 from Ciba companies, the Lowinox 44B25 from Great Lakes companies come from The ADK Stab AO-80 of Adeka Palmarole companies,

Stabilizer based on phosphorus, such as phosphite, such as the Irgafos 168 from Ciba companies,

- UV absorbents, such as the Tinuvin 312 from Ciba companies,

- HALS, as previously mentioned,

The stabilizer of amine type, such as the Naugard 445 from Crompton companies, or amine type of being obstructed stabilizer, Such as the Tinuvin 770 from Ciba companies,

Multifunctional stabilizer, such as the Nylostab S-EED from Clariant companies.

It is of course possible to imagine the mixture of two or more these organic stabilizers.

Preferably, the total weight relative to the ingredient of copolyamide, organic stabilizer is with the content of 0.3 to 3 weight % It is present in the copolyamide of layer (1) of the structure.

It states " inorganic stabilizers " and indicates the stabilizer based on copper.As the example of this kind of inorganic stabilizers, it can be mentioned that Be copper acetate and halogenation ketone.Incidentally, it can optionally consider other metals such as silver, but less have known to the metal Effect.These compounds based on copper are usually combined with alkali halide, particularly potassium halide.

When the structure must be in hot-air, especially to having improved length more than or equal to 100-120 DEG C of temperature When phase heat resistance, then these inorganic stabilizers are more particularly used, because it tends to prevent polymer chain scission.

More particularly, term " stabilizer based on copper " be intended to indicate that comprising at least one copper atom (especially ion or The copper atom of ionizable form, such as with complex form) compound.

Be present in the stabilizer based on copper in layer (1) can be selected from stannous chloride, copper chloride, cuprous bromide, copper bromide, Cuprous iodide, cupric iodide, cuprous acetate and copper acetate.It is mentioned that other metals such as halide of silver or acetate and base In the combination of the stabilizer of copper.These compounds based on copper are usually combined with alkali halide.One well-known reality Example is the mixture of CuI and KI, wherein CuI：KI ratios are usually 1:5 to 1:15.One example of this kind of stabilizer is to come from The Polyadd P201 of Ciba companies.

More detailed details about the stabilizer based on copper sees patent US 2 705 227.Stabilizer based on copper, Such as complex copper, it has recently emerged, such as Bruggolen H3336, H3337, H3373 from Br ü ggemann companies.

The stabilizer for being advantageously based on copper is selected from copper halide, copper acetate, copper halide or copper acetate and at least one alkali metal The mixture of halide and its mixture (CuI/KI) of mixture, preferably cupric iodide and potassium iodide.

Preferably, the total weight relative to the ingredient of copolyamide, based on the stabilizer of copper with 0.05 to 1.5 weight % Content be present in the layer (1) of the structure.

Preferably, copper (1) does not additionally comprise other transition metal.

Advantageously, present invention is accordingly directed to structures as defined above comprising at least one layer (1), layer (1) packet Containing MPMDT/XT copolyamides as defined above and include all the components relative to copolyamide and organic stabilizer weight The ratio of gauge is the impact modifying agent and/or core-shell type modifying agent of 5 to 35 weight %.

Advantageously, present invention is accordingly directed to structures as defined above comprising at least one layer (1), layer (1) packet Containing MPMDT/XT copolyamides as defined above and include relative to copolyamide and inorganic stabilizers, particularly based on copper The ratio of the weight meter of all the components of stabilizer is the impact modifying agent and/or core-shell type modifying agent of 5 to 35 weight %.

Advantageously, present invention is accordingly directed to structures as defined above comprising at least one layer (1), layer (1) packet Containing MPMDT/XT copolyamides as defined above and include (special relative to copolyamide and organic stabilizer and inorganic stabilizers Be not the stabilizer based on copper) mixture all the components weight meter ratio be 5 to 35 weight % impact modifying agent And/or core-shell type modifying agent.

Advantageously, present invention is accordingly directed to structures as defined above comprising at least one layer (1), layer (1) packet Containing MPMDT/XT copolyamides as defined above and include all the components relative to copolyamide and organic stabilizer weight The ratio of gauge is the impact modifying agent and/or core-shell type modifying agent of 5 to 25 weight %.

Advantageously, present invention is accordingly directed to structures as defined above comprising at least one layer (1), layer (1) packet Containing MPMDT/XT copolyamides as defined above and include (to be based particularly on copper relative to copolyamide and inorganic stabilizers Stabilizer) all the components weight meter ratio be 5 to 25 weight % impact modifying agent and/or core-shell type modifying agent.

Advantageously, present invention is accordingly directed to structures as defined above comprising at least one layer (1), layer (1) packet Containing MPMDT/XT copolyamides as defined above and include (special relative to copolyamide and organic stabilizer and inorganic stabilizers Be not the stabilizer based on copper) mixture all the components weight meter ratio be 5 to 25 weight % impact modifying agent And/or core-shell type modifying agent.

Advantageously, present invention is accordingly directed to structures as defined above comprising at least one layer (1), layer (1) packet Containing MPMDT/XT copolyamides as defined above and include all the components relative to copolyamide and organic stabilizer weight The ratio of gauge is the impact modifying agent and/or core-shell type modifying agent of 5 to 15 weight %.

Advantageously, present invention is accordingly directed to structures as defined above comprising at least one layer (1), layer (1) packet Containing MPMDT/XT copolyamides as defined above and include (to be based particularly on copper relative to copolyamide and inorganic stabilizers Stabilizer) all the components weight meter ratio be 5 to 15 weight % impact modifying agent and/or core-shell type modifying agent.

Advantageously, present invention is accordingly directed to structures as defined above comprising at least one layer (1), layer (1) packet Containing MPMDT/XT copolyamides as defined above and include (special relative to copolyamide and organic stabilizer and inorganic stabilizers Be not the stabilizer based on copper) mixture all the components weight meter ratio be 5 to 15 weight % impact modifying agent And/or core-shell type modifying agent.

Advantageously, in comprising impact modifying agent and/or the structure of core-shell type modifying agent and stabilizer, X is 1,10- Decamethylene diamine.

In an advantageous embodiment, the present invention relates to structures as defined above, wherein the layer (1) includes choosing From antistatic filler below：Carbon black, graphite, carbon fiber and carbon nanotube, especially carbon black and carbon nanotube.

In an advantageous embodiment, the present invention relates to structures as defined above, wherein the layer (1) can wrap Containing at least one additive selected from the following：Antioxidant, heat stabilizer, UV absorbents, light stabilizer, lubricant, mineral are filled out Material, fire retardant, nucleating agent, plasticizer and dyestuff.

Reinforcing fiber is excluded except additive, and especially term " mineral filler " does not include reinforcing fiber.

Advantageously, the total weight relative to the ingredient of layer (1), additive is with 1 to 20%, particularly 5 to 15% weight Amount ratio is present in layer (1).

In an advantageous embodiment, the present invention relates to structures as defined above, wherein there are the second layer (2), Layer (1) and (2) can adhere to each other.

" can adhere to each other " is stated it is meant that if the structure is formed by two layers, layer (1) and (2) are at least partly It adheres to each other.

If the structure includes at least one third layer, the third layer can be arranged layer (1) and layer (2) it Between, layer (1) and (2) do not adhere to each other in this case, but on the other hand, and layer (1) and (3) adhere to each other, layer (3) and (2) it also adheres to each other.

Advantageously, which is made of two layers (1) adhered to each other and (2).

Advantageously, the layer (2) includes at least one selected from aliphatic polyamide and aromatic polyamides, particularly aliphatic polyamides The polyamide of amine.

Advantageously, the aliphatic polyamide is by least one lactams or at least one amino carboxylic acid or diamines and dicarboxylic acids Or mixtures thereof polycondensation obtain, the diamines is selected from aliphatic diamine and alicyclic diamine and dicarboxylic acids be selected from aliphatic diacid and Or mixtures thereof alicyclic diacids.

Amino carboxylic acid can be selected from 9 aminononanoic acid, 10- aminocapric acids, 12 amino dodecanoic acid and 11- amino-undecanoics Acid and its derivative, especially N- heptyl -11- amino undecanoic acids, it is advantageously that 12 amino dodecanoic acid and 11- amino ten One alkanoic acid.

Lactams can be selected from pyrrolidones, 2- piperidones, caprolactam, oenantholcatam, spicy inner formyl amine, nonyl lactams, Caprinolactam, hendecane lactams and lauryl lactam, it is advantageously that hendecane lactams and lauryl lactam.

When diamines is aliphatic and straight chain, with formula H₂N-(CH₂)_a-NH₂.Diacid can be that aliphatic series is (especially straight Chain aliphatic series), alicyclic or aromatics.

Preferably, when diamines is straight chain and aliphatic series, selected from butanediamine (a=4), pentanediamine (a=5), hexamethylene diamine (a =6), heptamethylene diamine (a=7), octamethylenediamine (a=8), nonamethylene diamine (a=9), decamethylene diamine (a=10), hendecane diamines (a=11), Dodecamethylene diamine (a=12), tridecane diamine (a=13), tetradecane diamines (a=14), hexadecane diamines (a=16), 18 Alkane diamines (a=18), octadecamethylene diamine (a=18), eicosane diamines (a=20), docosane diamines (a=22) and by dimerization The diamines that aliphatic acid obtains.

When diamines is alicyclic, it is preferably selected from alicyclic comprising two rings.It is particularly corresponding to following general formula：

Wherein：

-R₁、R₂、R₃And R₄The group selected from hydrogen atom or the alkyl with 1 to 6 carbon atom is independently represented,

The bivalent group that-X represents singly-bound or is made up of：

Include the linear chain or branched chain aliphatic chain of 1 to 10 carbon atom, optionally by alicyclic with 6 to 8 carbon atoms Or aromatic group substitution,

Alicyclic group with 6 to 12 carbon atoms.

It is highly preferred that the Ca alicyclic diamines of polyamide are selected from bis- (3,5- dialkyl group -4- aminocyclohexyls) methane, double (3,5- dialkyl group -4- aminocyclohexyls) ethane, bis- (3,5- dialkyl group -4- aminocyclohexyls) propane, bis- (3,5- dialkyl group - 4- aminocyclohexyls) butane, bis- (3- methyl -4- aminocyclohexyls) methane (being denoted as BMACM, MACM or B), to bis- (amino rings Hexyl) methane (PACM) and isopropylidene two (cyclohexylamine) (PACP).

In " Cycloaliphatic Amines " (encyclopedia of chemical technology (Encyclopedia of Chemical Technology), Kirk-Othmer, the 4th edition (1992), the 386-405 pages) in give the non-poor of these alicyclic diamines Lift list.

Aliphatic series and unbranched dicarboxylic acid are selected from succinic acid (b=4), glutaric acid (b=5), adipic acid (b=6), pimelic acid (b= 7), suberic acid (b=8), azelaic acid (b=9), decanedioic acid (b=10), heneicosanedioic acid (b=11), dodecanedioic acid (b= 12), tridecandioic acid (b=13), tetracosandioic acid (b=14), hexadecandioic acid (hexadecane diacid) (b=16), octadecanoid acid (b=18), ten Eight carbene diacid (b=18), eicosane diacid (b=20), docosandioic acid (b=22) and the aliphatic acid two containing 36 carbon Aggressiveness.

Above-mentioned fat acid dimer be by unsaturated unary fatty acid with long hydrocarbon chain (such as linoleic acid and Oleic acid) the dimer (fatty acid) yl that obtains of oligomeric or polymerization, as particularly described in document EP 0 471566.

Can include following carbon skeleton when diacid is alicyclic：Norbornane methylmethane, cyclohexyl-methane, two rings Hexyl methane, dicyclohexyl propane, two (methylcyclohexyl) propane.

The polyamide of layer (2) can be homopolyamide or copolyamide.

Term for defining polyamide is recorded in standard ISO 16396-1:2015“Plastics--Polyamide (PA)molding and extrusion materials--Part 1:Designation system,marking of products and basis for specifications”。

Advantageously, the polyamide of layer (2) is selected from PA11, PA12, PA1010, PA1012, PA610 and PA612.

In an advantageous embodiment, the present invention relates to structures as defined above, wherein the polyamide with layer (2) Other different polyamide can reside in layer (2).

Other described polyamide are as defined in layer (2), condition is that it is different from the polyamide of layer (2) above.

Advantageously, plasticizer is present in layer (2).

Advantageously, the plasticizer of layer (2) is with the 1 to 20 of the weight meter of all the components of the copolyamide relative to layer (2) The weight weight of %, particularly 5 to 15 % exists.

In an advantageous embodiment, the present invention relates to structure as defined above, wherein impact modifying agent and/or Core-shell type modifying agent is present in layer (2).

Impact modifying agent and/or core-shell type modifying agent are as defined above.

Advantageously, the weight meter relative to all the components of the copolyamide of layer (2), impact modifying agent and/or core-shell type The amount of modifying agent is 5 to 35 weight %, especially 5 to 25 weight %, and more particularly 5 to 15 weight %.

In an advantageous embodiment, the present invention relates to structures as defined above, wherein there are the second layer (2), Layer (1) and (2) adheres to each other, and layer (1) is one of layer defined above, and layer (2) optionally includes other polyamide, layer (2) plasticizer and ratio of 1 to 20 weight % of the weight meter of all the components comprising the copolyamide relative to layer (2) is 5 To the impact modifying agent and/or core-shell type modifying agent of 35 weight %.

In an advantageous embodiment, the present invention relates to structures as defined above, wherein there are the second layer (2), Layer (1) and (2) adheres to each other, and layer (1) is one of layer defined above, and layer (2) optionally includes other polyamide, layer (2) plasticizer and ratio of 1 to 20 weight % of the weight meter of all the components comprising the copolyamide relative to layer (2) is 5 To the impact modifying agent and/or core-shell type modifying agent of 25 weight %.

In an advantageous embodiment, the present invention relates to structures as defined above, wherein there are the second layer (2), Layer (1) and (2) adheres to each other, and layer (1) is one of layer defined above, and layer (2) optionally includes other polyamide, layer (2) plasticizer and ratio of 5 to 15 weight % of the weight meter of all the components comprising the copolyamide relative to layer (2) is 5 To the impact modifying agent and/or core-shell type modifying agent of 35 weight %.

In an advantageous embodiment, the present invention relates to structures as defined above, wherein there are the second layer (2), Layer (1) and (2) adheres to each other, and layer (1) is one of layer defined above, and layer (2) optionally includes other polyamide, layer (2) plasticizer and ratio of 5 to 15 weight % of the weight meter of all the components comprising the copolyamide relative to layer (2) is 5 To the impact modifying agent and/or core-shell type modifying agent of 25 weight %.

In an advantageous embodiment, the present invention relates to structures as defined above, wherein there are the second layer (2), The wherein described layer (2) includes stabilizer selected from the following：Organic stabilizer, inorganic stabilizers (are based particularly on the stabilization of copper Agent) and its mixture.

Stabilizer is as defined above.

In an advantageous embodiment, the present invention relates to structures as defined above, wherein there are the second layer (2), Its middle level (1) includes organic stabilizer, and layer (2) includes inorganic stabilizers, particularly the stabilizer based on copper.

In an advantageous embodiment, the present invention relates to structures as defined above, wherein there are the second layer (2), Its middle level (1) includes inorganic stabilizers, particularly the stabilizer based on copper, and layer (2) includes organic stabilizer.

In an advantageous embodiment, the present invention relates to structures as defined above, wherein there are the second layer (2), The wherein described layer (2) includes antistatic filler selected from the following：Carbon black, graphite, carbon fiber and carbon nanotube, especially carbon black and Carbon nanotube.

In an advantageous embodiment, the present invention relates to structures as defined above, wherein there are the second layer (2), The wherein described layer (2) can include at least one additive selected from the following：Antioxidant, heat stabilizer, UV absorbents, light are steady Determine agent, lubricant, mineral filler, fire retardant, nucleating agent and dyestuff.

In an advantageous embodiment, the present invention relates to structures as defined above, and middle level (1) is barrier layer, Especially to the barrier layer of fluid, the fluid is selected from fuel, and the fuel is gasoline, particularly biogasoline (gasoline and alcohol The especially mixture of methanol or ethyl alcohol) or diesel oil, particularly biodiesel, oil, brake fluid, urea liquid be based on glycol (glycol) cooling fluid, gas, particularly compressed air, and the barrier layer (1) is contacted with fluid.

Therefore, the structure defined in this embodiment include at least one layer (1) and therefore can be single layer or Double-deck (1) and (2), but if the structure includes other layers, this does not deviate by present disclosure.

Advantageously, which is made of two layers (1) and (2), and layer (1) is barrier layer.

Therefore, include with lower layer from external-to-internal in the case where the structure includes two layers：(2)//(1).

In the case where the structure includes at least one other layer, other layers cannot be contacted with fluid.

In an advantageous embodiment, the present invention relates to including at least one layer (1) as defined above and as above fixed The structure of the second layer (2) of justice, middle level (1) and (2) can adhere to each other,

Layer (3) is additionally included, middle level (3) and layer (1) are identical or different.

In this embodiment, the structure from external-to-internal include with lower layer or by being formed with lower layer：

(3) // (2) // (1) or (2) // (3) // (1).

Advantageously, layer (3) is different from layer (1) and is articulamentum (tie layer), and the structure is from outside to interior Portion includes with lower layer：(2) // (3) // (1), middle level (1) are contacted with fluid.

Advantageously, in structure (2) // (3) // (1), the thickness of layer (1) is 100 to 300 μm, especially 200 to 300 μm, especially 250 μm, the thickness of layer (3) is 50 to 100 μm or 100 to 200 μm, especially 150 μm, and the thickness of layer (2) It is 50 to 800 μm, especially 50 to 200 μm or 500 to 700 μm.

Articulamentum can be mixture below：The average carbon atom number of at least one each nitrogen-atoms is 4 to 8.5, has It is 4 to 7 polyamide sharply；The average carbon atom number that at least one fusing point is greater than or equal to 180 DEG C and each nitrogen-atoms be 7 to 10, it is 9 to 18, favorably to be advantageously 7.5 to 9.5 polyamide and the average carbon atom number of at least one each nitrogen-atoms The polyamide that ground is 10 to 18, particularly as defined in document WO 09/122060.

In an advantageous embodiment, the present invention relates to including at least one layer (1) as defined above, as defined above The second layer (2) (layer (1) and (2) can adhere to each other) and layer (3) (layer (3) with layer (1) identical or different) structure,

The structure additionally includes at least one other layer (4), and middle level (1) is contacted with fluid.

Advantageously, layer (4) is the layer of EVOH.

In an advantageous embodiment, the present invention relates to including at least one layer (1) as defined above and as above fixed The second layer (2) (layer (1) and (2) can adhere to each other) and layer (3) (layer (3) and layer (1) identical or different) of justice and at least The structure of one other layer (4), middle level (1) are contacted with fluid, the structure from external-to-internal include with lower layer： (2) // (4) // (3) // (1), middle level (1) are contacted with fluid.

Advantageously, in structure (2) // (4) // (3) // (1), layer (3) is articulamentum as defined above.

Advantageously, in structure (2) // (4) // (3) // (1), layer (4) is the layer of EVOH as defined above.

Advantageously, in structure (2) // (4) // (3) // (1), layer (3) is articulamentum as defined above and layer (4) It is the layer of EVOH as defined above.

Advantageously, which is made of layer as defined above (2) // (4) // (3) // (1).

In an advantageous embodiment, the present invention relates to including at least one layer (1) as defined above, as defined above The second layer (2) (layer (1) and (2) can adhere to each other), layer (3) (layer (3) with layer (1) identical or different), it is at least one its The structure of his layer (4), middle level (1) are contacted with fluid, and from external-to-internal include with lower layer：(2)//(4)// (3) // (1), middle level (1) are contacted with fluid.

The structure additionally includes articulamentum (3 '), identical or different with articulamentum (3).

Therefore layer (3 ') be with above for the identical articulamentum of type defined in layer (3), but with identical or different Composition.

Advantageously, additionally include the structure of articulamentum (3 ') from external-to-internal include with lower layer：(2)// (3 ') // (4) // (3) // (1), middle level (1) are contacted with fluid.

Advantageously, the thickness of layer (1) is 100 to 200 μm, especially 150 μm, and the thickness of layer (2) is 100 to 200 μm, special It it is not 150 μm, the thickness of layer (3) is 200 to 400 μm, especially 300 μm, and the thickness of layer (3 ') is 200 to 400 μm, especially 300 μm, and the thickness of layer (4) is 50 μm to 150 μm, especially 100 μm.

The present invention relates to the bottle, tank, container, pipe and the storages that are manufactured with one of structure as defined above according to another aspect, Slot.

The present invention relates to what is be made of the film manufactured with one of structure as defined above to pack according to another aspect,.

The present invention relates to MPMDT/XT polyamide to be used to prepare including at least one comprising described according to another aspect, The structure of the barrier layer (1) of MPMDT/XT polyamide, particularly the purposes of multilayer structure making, wherein：

Condition is that MPMD is not substituted completely,

The composition is free of reinforcing fiber.

All features and all embodiments defined above for the structure can be adapted for use defined above On the way.

Embodiment：

1) MPMDT/10T and comparison polyamide are prepared

5kg or less raw materials are introduced in 14 raising pressure autoclave reactors：

- 500g water,

One or more diamines,

Amino acid (optional),

One or more diacid,

Simple function chain regulator：It is suitable for the benzoic acid or stearic acid of the amount of target viscosities,

Sodium hypophosphites of-the 35g in solution,

- 0.1g Wacker AK1000 antifoaming agent (Wacker Silicones).

The following table 1 gives the molecular configuration and partial property and molar ratio of polyamide (by reference to test).

Remaining oxygen in closed reactor is removed, 230 DEG C of temperature is then heated to for introduced material. After being stirred 30 minutes under the conditions of these, the steam under pressure formed in the reactor is made gradually to be depressurized in 60 minutes, while by Cumulative plus material temperature makes it be established at atmosheric pressure at Tm+10 DEG C.Then continue to polymerize under the flushing of the nitrogen of 20l/h Until obtaining target viscosities shown in mark sheet.

Then polymer is poured out by bottom valve, is then cooled down in the sink, is then granulated.

Then using equal to Tm+20 DEG C injection temperature and be heated to 100 DEG C of mold by injection press by product with The form injection molding of the plate of 100mm × 100mm × 1mm.By imperfect crystal (according to ISO 11357-2：2013 add in DSC There is recrystallization when hot) plate anneal at Tg+30 DEG C under vacuum 2h.

The measurement of inherent viscosity or intrinsic viscosity carries out in metacresol.This method is to those skilled in the art It is well known.Follow standard ISO 307:2007, but change solvent (using metacresol rather than sulfuric acid), temperature be 20 DEG C with And a concentration of 0.5 weight %.

According to standard ISO 11357-2:2013, after second of heating process, use differential scanning calorimetry (DSC) (DSC) glass transition temperature Tg of thermoplastic polymer used in measuring.Heating and cooling velocity are 20 DEG C/min.

According to standard ISO 11357-3:2013, after first time heats, pass through dsc measurement fusing point Tm and crystallization temperature Spend Tc.Heating and cooling velocity are 20 DEG C/min.

According to standard ISO 11357-3:2013 measure the matrix polymer by differential scanning calorimetry (DSC) Crystallization heat.

The content of amine and sour chain end is measured by H NMR spectroscopy.

According to gravimetric method CE10 at 60 DEG C：Isooctane/toluene/ethanol=45/45/10 volume % and CE85：It is different pungent Alkane/toluene/ethanol=7.5/7.5/85 volumes % measures the measured value to the permeability of gasoline.

During induction, instantaneous permeability is zero, is then gradually increased to equilibrium valve, corresponds to continuous operation condition Lower permeability value.The value obtained under the conditions of continuous operation is considered as the permeability of material.

As a result it is shown in the following table 1.

Compared with comparative example, the compound of the present invention shows improved permeability.

Claims

1. the barrier structure body selected from bottle, tank, container, pipe, storage tank and film comprising at least one to be copolymerized acyl comprising MPMDT/XT The barrier layer (1) of amine, wherein：

MPMDT is existed with 5 to 50%, particularly 5 to 45%, preferably 15 to 45%, more preferable 20 to 45% molar content Composition amide moieties unit, wherein MPMD represents 2- methyl pentamethylene diamines (MPMD) and T represents terephthalic acid (TPA),

XT is with existing for 50 to 95%, particularly 55 to 95%, preferably 55 to 85%, more preferable 55 to 80% molar content The unit of main amide moieties is constituted, wherein X is C₉To C₁₈, preferably C₉、C₁₀、C₁₁And C₁₂Linear aliphatic diamines, and wherein T It is terephthalic acid (TPA),

In MPMDT and/or XT units, independently of each other, based on the total amount of dicarboxylic acids, up to 30mol% to benzene Dioctyl phthalate available other aromatics, aliphatic series or alicyclic dicarboxylic acid comprising 6 to 36 carbon atoms, particularly 6 to 14 carbon atoms It substitutes, and

In MPMDT and/or XT units, independently of each other, based on the total amount of diamines, the up to MPMD of 30mol% And/or X in appropriate circumstances can be replaced with other diamines comprising 4 to 36 carbon atoms, particularly 6 to 12 carbon atoms Generation, and

In copolyamide, based on the total amount of monomer, it can be formed by lactams or amino carboxylic acid no more than 30mol%, And

Condition is, based on the total amount of the monomer used in copolyamide, substitutes the monomer of terephthalic acid (TPA), MPMD and X Summation is no more than the concentration of 30mol%, and

Condition is that MPMD is not substituted completely,

The composition is free of reinforcing fiber.

2. barrier structure body as described in claim 1, wherein glass transition temperature Tg >=125 DEG C of the copolyamide, Particularly glass transition temperature Tg>125 DEG C, according to standard ISO 11357-2:2013 measure.

3. barrier structure body as claimed in claim 1 or 2, wherein X is 1,10- decamethylene diamines.

4. the barrier structure body as described in one in claims 1 to 3, wherein the monomer of the copolyamide it is unused other Diamines, other dicarboxylic acids or lactams substitute.

5. the barrier structure body as described in one in Claims 1-4, wherein the layer (1) include impact modifying agent and/or Core-shell type modifying agent.

6. the barrier structure body as described in one in claim 1 to 5, wherein the structure is made of single layer (1).

7. the barrier structure body as described in one in claim 1 to 6, wherein the layer (1) includes stabilization selected from the following Agent：Organic stabilizer, inorganic stabilizers, particularly the stabilizer based on copper and its mixture.

8. the barrier structure body as described in one in claim 1 to 7, wherein the layer (1) includes selected from the following anti-quiet Electric filler：Carbon black, graphite, carbon fiber and carbon nanotube, especially carbon black and carbon nanotube.

9. the barrier structure body as described in one in claim 1 to 8, wherein the layer (1) can include at least one choosing From additive below：Antioxidant, heat stabilizer, UV absorbents, light stabilizer, lubricant, mineral filler, fire retardant, at Core agent, plasticizer and dyestuff.

10. the barrier structure body as described in one in claim 1 to 5 and 7 to 9, wherein there are the second layer (2), layer (1) and (2) it can adhere to each other.

11. barrier structure body as claimed in claim 10, wherein the layer (2) include it is at least one selected from aliphatic polyamide and The polyamide of aromatic polyamides, particularly aliphatic polyamide.

12. the barrier structure body as described in claim 10 or 11, wherein the aliphatic polyamide is by least one lactams, one Kind of amino carboxylic acid or diamines and dicarboxylic acids, or mixtures thereof polycondensation obtain, the diamines be selected from aliphatic diamine, aromatic diamine and Alicyclic diamine and dicarboxylic acids are selected from aliphatic diacid, aromatic diacid and alicyclic diacids.

13. the aliphatic polyamide of the barrier structure body as described in one in claim 10 to 12, middle level (2) is selected from PA11, PA12, PA1010, PA1012, PA610 and PA612.

14. the barrier structure body as described in one in claim 10 to 13, wherein other different from the polyamide of layer (2) Polyamide can reside in layer (2).

15. the structure as described in one in claim 10 to 14, wherein plasticizer are present in layer (2).

16. the barrier structure body as described in one in claim 10 to 15, wherein impact modifying agent are present in layer (2).

17. the barrier structure body as described in one in claim 10 to 16, wherein the layer (2) includes selected from the following steady Determine agent：Organic stabilizer, inorganic stabilizers, particularly the stabilizer based on copper and its mixture.

18. the barrier structure body as described in one in claim 10 to 17, middle level (1) includes organic stabilizer, and Layer (2) includes inorganic stabilizers, particularly the stabilizer based on copper.

19. the structure as described in one in claim 10 to 18, middle level (1) includes inorganic stabilizers, particularly base In the stabilizer of copper, and layer (2) includes organic stabilizer.

20. the barrier structure body as described in one in claim 10 to 19, wherein the layer (2) includes selected from the following anti- Electrostatic filler：Carbon black, graphite, carbon fiber and carbon nanotube, especially carbon black and carbon nanotube.

21. the barrier structure body as described in one in claim 10 to 20, wherein the layer (2) can include at least one Additive selected from the following：Antioxidant, heat stabilizer, UV absorbents, light stabilizer, lubricant, mineral filler, fire retardant, Nucleating agent and dyestuff.

22. the barrier structure body as described in one in claim 1 to 21, middle level (1) is barrier layer, especially to fluid Barrier layer, the fluid is selected from fuel, the fuel be gasoline, particularly biogasoline (gasoline and alcohol especially methanol or The mixture of ethyl alcohol) or diesel oil, particularly biodiesel, oil, brake fluid, urea liquid, the cooling fluid based on glycol, Gas, particularly compressed air, barrier layer (1) are contacted with fluid.

23. the barrier structure body as described in one in claim 10 to 22, additionally include layer (3), middle level (3) with Layer (1) is identical or different.

24. barrier structure body as claimed in claim 23, middle level (3) are different from layer (1) and are articulamentums, and the knot Structure body from external-to-internal include with lower layer：(2) // (3) // (1), layer (1) are contacted with fluid.

25. the barrier structure body as described in one in claim 23 and 24, wherein there are at least one other layer (4), layer (1) it is contacted with fluid.

26. the barrier structure body as described in one in claim 23 to 25, middle level (4) are the layers of EVOH.

27. the barrier structure body as described in one in claim 23 to 26, the wherein structure include from external-to-internal With lower layer：(2) // (4) // (3) // (1), layer (1) are contacted with fluid.

28. the barrier structure body as described in claim 25 or 26, wherein there are articulamentum (3 '), it is identical as articulamentum (3) Or it is different.

29. the barrier structure body as described in one in claim 25 to 28, the wherein structure include from external-to-internal With lower layer：(2) // (3 ') // (4) // (3) // (1), layer (1) are contacted with fluid.

30. the bottle manufactured with structure as described in any one of the preceding claims, tank, container, pipe and storage tank.

31. being packed by what the film manufactured with structure as described in any one of the preceding claims was constituted.

32. MPMDT/XT copolyamides are used to prepare barrier structure body, particularly multilayer barrier as defined in claim 1 The purposes of structure, the barrier structure body include at least one barrier layer (1) for including the MPMDT/XT copolyamides, institute It states barrier structure body and is selected from bottle, tank, container, pipe, storage tank and film.